Phosphorus, nitrogen and sulfo-containing additives

ABSTRACT

Additives made by reaction of (A) at least one phosphorus acid compound of the formula: ##STR1## wherein each X is independently oxygen or divalent sulfur, M is hydrogen or an equivalent of metal or ammonium cation, R is a hydrogen atom or a hydrocarbyl or hydrocarbyloxy or hydrocarbyl mercapto group of about one to about thirty carbon atoms and R&#39; is XM or R with the proviso that the total number of carbon atoms in both R and R&#39; is at least two, with (B) at least one sulfo-containing compound of the formulae: ##STR2## wherein y is one or two, R 3  is hydrogen or lower alkyl group, R 2  is a divalent or trivalent hydrocarbyl group, R 4  is a trivalent hydrocarbyl group, and Q is --OH, --OR 3 , --OM, an alkylene polyamine residue, or N(R 3 ) 2 , are novel and useful and have utility as, for example, additives for water-containing hydraulic fluids.

REFERENCE TO RELATED APPLICATIONS

This application is a division of Ser. No. 424,246, filed Dec. 12, 1973now U.S. Pat. No. 3,926,821.

FIELD OF THE INVENTION

This invention relates to new compositions of matter and to lubricatingand functional fluids containing them. More particularly, thecompositions of this invention are additives made by the reaction ofcertain phosphorus acid compounds with certain sulfo-containingcompounds. This invention also relates to lubricant and hydraulic fluidcompositions comprising these additives as well as processes forpreparing the additives.

BRIEF DESCRIPTION OF THE PRIOR ART

The use of sulfo-, nitrogen-, and phosphorus-containing compositions asadditives for lubricants and functional fluids to improve one or moreperformance characteristics of such materials is well known. Among thefunctional fluids whose properties can be so improved are aqueoushydraulic fluids. Some hydraulic fluids are based on mixtures of glycol,water and oil, while others are based on oil-water emulsions. Regardlessof their specific type, these aqueous hydraulic fluids are particularlyuseful in areas where fire resistance is of prime concern, such as onships, in steel mills, etc. It is desirable to impart extreme pressureproperties to such aqueous hydraulic fluids and it is an advantage ofthis invention that through its practice this can be done.

Further general background on the use of aqueous hydraulic fluids, theirproperties and compositions can be found in "Lubrication" Vol. 48, 161(1962) published by Texaco Inc. of N.Y., N.Y., Which is expresslyincorporated herein for its background information and discussion ofaqueous hydraulic fluids.

It is known that various types of phosphorus acids can be reacted withunsaturated carboxylic acid derivatives such as acrylamides and nitratocompounds (see for example, U.S. Pat. Nos. 2,709,156, 2,742,431,2,766,208, and 3,098,824). It has not been previously known orsuggested, however, that phosphorus acid compounds can be reacted withsulfo-, nitrogen-containing olefinic compounds to produce the additivecompositions of this invention or to incorporate those additivecompositions in lubricant and functional fluid compositions such asthose of the present invention.

SUMMARY OF THE INVENTION

A novel class of phosphorus-, sulfo-, and nitrogen-containing productswhich are useful as additives for lubricants and functional fluids,particularly aqueous hydraulic fluids, has been found. These additivesare made by reacting certain phosphorus acid compounds with sulfo- andnitrogen-containing olefinic substrates. Aqueous hydraulic fluidcompositions prepared by combining these additives with glycol-water andoil-water emulsion fluids are within the scope of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The phosphorus acid compounds, (A) used as addends in making theadditives of the present invention are of the formula: ##STR3## whereineach X is independently oxygen or divalent sulfur, M is hydrogen or anequivalent of a metal or ammonium cation, R is hydrogen or ahydrocarbyl, hydrocarbyloxy or hydrocarbyl mercapto group of about oneto about thirty carbon atoms and R' is XM or R, with the proviso thatthe total number of carbon atoms in both R and R' is at least two.Preferably each X is oxygen and each R and R' contains between one andeighteen carbon atoms and is substantially aliphatic in nature; morepreferably both R and R' are independently C₁₋₁₈ alkoxy groups and eachX is a divalent sulfur atom.

When reference in this specification and the appended claims is made tohydrocarbyl, hydrocarbyloxy, hydrocarbyl mercapto, aliphatic or alkylgroups, it is to be understood, unless expressly stated to the contrary,that reference is also being made to substantially hydrocarbyl,substantially hydrocarbyloxy, substantially hydrocarbyl mercapto,substantially aliphatic, and substantially alkyl groups. The descriptionof these groups as being substantially hydrocarbyl means that theycontain no non-hydrocarbyl substituents which would significantly affectthe principal hydrocarbyl characteristics or properties of the grouprelevant to their uses as described herein. Thus, it is obvious, forexample, in the context of this invention, that a purely hydrocarbyl C₂₀alkyl group and a C₂₀ alkyl group substituted with a methyl mercapto ormethoxyl substituent at a point in the chain remote from other polar(i.e., non-hydrocarbyl) groups, would be substantially similar in itsproperties with regard to its use in this invention, and would in factbe recognized as art equivalents by those of ordinary skill in the art.That is, one of ordinary skill in the art would recognize both suchgroups to be substantially hydrocarbyl, etc.

Non-limiting examples of substituents which do not significantly alterthe hydrocarbyl, etc., properties or nature of hydrocarbyl, etc., groupsof this invention are the following:

Ether groups (especially hydrocarbyloxy and particularly alkoxy groupsof up to ten carbon atoms)

Amino groups (including mono- and disubstituted aminos such as mono- anddialkyl amino or mono- and diaryl amino and the like, e.g., ethyl amino,dimethyl amino, diheptyl amino, cyclohexyl amino, benzyl amino, etc.)

Oxo groups (e.g., ##STR4## such as in ketones and aldehydes)

Oxa groups (e.g., --O-- linkages in the main carbon chain)

Nitro groups

Imino groups (e.g., ##STR5## linkages in the main carbon chain)

Cyano groups

Fluoro groups

Chloro groups

Thioether groups (especially C₁₋₁₀ alkyl thioether)

Thia groups (e.g., -S- linkages in the main carbon chain)

Carbohydrocarbyloxy groups (e.g., ##STR6## hydrocarbyl)

Sulfonyl groups

Sulfinyl groups

This list is intended to be merely illustrative and not exhaustive andthe omission of a certain class of substituent is not meant to requireits exclusion.

In general, if such substituents are present, it will be found that notmore than two for each ten carbon atoms in the hydrocarbyl group andpreferably not more than one for each ten carbon atoms, will notsubstantially affect the hydrocarbyl nature of the group. Nevertheless,the hydrocarbyl, hydrocarbyloxy, hydrocarbyl mercapto, etc., groupsusually will be free from non-hydrocarbon groups due to economicconsiderations.

In the above formula, R and R' can be saturated or unsaturated andinclude alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, cycloalkenyl,etc. Suitable specific groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, amyl, isoamyl, n-hexyl, 2-ethylhexyl,4-methyl-2-pentyl, cyclohexyl, chlorocyclohexyl, methyl-cyclohexyl,heptyl, n-octyl, tertiary octyl, nonyl, lauryl, cetyl, phenyl,bromophenyl, 2,4-dichlorophenylethyl, chlorophenyl, nitrophenyl,methoxyphenyl, ethylphenyl, propylphenyl, butylphenyl,benzylphenylethyl, octenyl, cyclohexenyl, ethyl cyclopentyl,N,N'-dibutylamino propyl phenyl, 3-nitro octyl, p-carbothoxy phenyl,phenoxyphenyl, naphthyl, alkylated naphthyl such as propylenetetramer-substituted naphthyl, acetyl phenyl, 2-ethoxyethyl, 6-ethylamino heptyl, 4-cyanophenyl, 3,3,3-trifluoropropyl, dichloromethyl3-thia-n-octyl, 2-methyl mercapto naphthyl, 4-ethyl sulfonyl-n-butyl,4-phenylsulfinyl, phenyl, etc.

Methods of the preparation of such phosphorus acid compounds are wellknown to those of skill in the art and need not be repeated here. Forconvenience, however, reference is made to "Organo-PhosphorusCompounds", by G. M. Kosolapoff, John Wiley Publishers, 1950, New York,which is incorporated herein by reference for its disclosure of methodsfor preparing these phosphorus acid compounds.

A particularly preferred type of phosphorus acid compound which may beused in this invention is prepared by the reaction of phosphoruspentasulfide or homologs thereof (e.g., P₄ S₁₀) with hydroxy compoundswhich contain the organic groups R and R' as defined above. An exampleof this type of reaction is the reaction of phosphorus pentasulfide withethyl alcohol to produce, 0,0-diethyl phosphorodithioic acid.

Metal or ammonium salts of the above phosphorus acids can be preparedquite conveniently by neutralization techniques well known to those ofskill in the art, such as treating the particular acid with a metaloxide, metal or ammonium hydroxide. Thus, for example, the calcium saltof the afore-described 0,0-diethyl phosphorodithioic acid can beprepared by reacting the acid with calcium oxide. Similarly, thetetramethyl ammonium salt can be prepared by reaction of the same acidwith tetramethyl ammonium hydroxide.

As noted above, M represents one equivalent of a metal or ammoniumcation. Such metal cations are derived from Groups I(A), I(B), II(A),II(B), III(A), and VIII of the periodic table. When M represents anammonium cation, it can also be represented as N⁺(R³)₄, (R³ beingdefined below), that is a mono-ammonium salt.

The sulfo- and nitrogen-containing compounds, (B), used in thepreparation of the additive compositions of this invention are of thegeneral formulae: ##STR7## wherein y is one or two, each R³ isindependently hydrogen or a lower alkyl group of one to seven carbons,R² is a di- or trivalent hydrocarbyl group having one to eighteen carbonatoms, R⁴ is a trivalent hydrocarbyl group having one to eighteen carbonatoms, and Q is selected from the group consisting of --OH, --OR³, --OM,-O(Alkylene-O)_(n) -R³, ##STR8## wherein n has an average value of aboutone to about ten, and the alkylene group has from one to ten carbonatoms.

When R² is a divalent hydrocarbyl group the following illustrate some ofthe groups within the scope of this invention (where a named group hasseveral isomeric forms (e.g., butylene), all such forms are included):

    ______________________________________                                         Methylene                                                                                     Ethylene#Cyclohexylene                                       Propylene        Cyclopentylene                                               Butylene         Methylcyclopentylene                                          Hexylene                                                                                       Octylene#                                                                    Decylene#Hexadecylene                                        CHCH             CHCHCH.sub.2                                                 Tolylene##                                                                    Phenylene        Naphthylene                                                  Xylylene         C.sub.6 H.sub.4 (CH.sub.2).sub.11 CH.sub.2                   C.sub.6 H.sub.2 (C.sub.2 H.sub.4).sub.2                                        ##STR13##                                                                     ##STR14##                                                                    ______________________________________                                    

Trivalent radicals such as R² and R⁴ are similar to the above but havean additional hydrogen atom abstracted.

Many obvious variations of these radicals will be apparent to those ofskill in the art and are included within the scope of the invention.

Preferably, Q is --OH or --OM that is, one equivalent of a cationderived from a Group I(A), I(B), II(A), II(B), III(A) or VIII metal oramine or polyamine.

Often it is preferred that the Q be derived by neutralization from analkylene polyamine of the formula: ##STR15## wherein n has an averagevalue between about one and about ten and the alkylene group is a loweralkylene group of one to ten carbon atoms. As noted above, R³ is analiphatic or hydroxy-substituted aliphatic group of up to about sevencarbon atoms; often the alkylene group contains between two and aboutsix carbon atoms.

Such alkylene polyamines include methylene polyamines, ethylenepolyamines, butylene polyamines, propylene polyamines, pentylenepolyamines, etc. The higher homologs and related heterocyclic aminessuch as piperazines and N-amino alkyl substituted piperazines are alsoincluded. Specific examples of such polyamines are ethylene diamine,triethylene, tetramine, tris-(2-aminoethyl)amine, propylene diamine,trimethylene diamine, tripropylene tetramine, tetraethylene pentamine,heptaethylene hexamine, etc.

Higher homologs obtained by condensing two or more of the above-notedalkylene amines are similarly useful as are mixtures of two or more ofthe afore-described polyamines.

Ethylene polyamines, such as some of those mentioned above, areespecially useful for reasons of cost and effectiveness. Such polyaminesare described in detail under the heading Ethylene Amines in KirkOthmer's "Encyclopedia of Chemical Technology", 2d Edition, Vol. 7,pages 22-37, Interscience Publishers, New York (1965). Such polyaminesare most conveniently prepared by the reaction of ethylene dichloridewith ammonia or by reaction of an ethylene imine with a ring openingreagent such as water, ammonia, etc. These reactions result in theproduction of a complex mixture of polyalkylene polyamines includingcyclic condensation products such as the aforedescribed piperazines.Ethylene polyamine mixtures are particularly useful in preparing thecompositions of this invention due to reasons of economy andavailability. On the other hand, quite satisfactory products can also beobtained by the use of the pure polyamines themselves.

The sulfo-products derived from the amines and polyamines describedabove can be ammonium salts, dehydrated derivatives of such salts andmixtures thereof, depending on the reaction conditions used to preparethem. Variation of the reaction conditions to produce the desired typeof product is well within the skill of the ordinary worker in the art.When the sulfo-product is an ammonium salt, it can be represented by theabove formula in which ##STR16##

As noted above, Q in the formula of the sulfo-nitrogen-containingcompound of this invention can be --OR³ or O-(Alkylene-O)_(n) R³. Suchcompounds are, of course, esters of the corresponding monohydric (e.g.,HOR³) and polyhydric (e.g., HO-(Alkylene-O)_(n) R³) alcohols. They canbe prepared by a variety of techniques known to those of skill in theart, such as esterification (with or without conventional esterificationcatalyst), ester exchange, reaction with epoxides, etc. Usually esterswill be prepared by heating a sulfonic acid with a monohydric alcohol,polyhydric alcohol, etc. Generally, the esters will be derived frommonohydric alcohols of 1 to 7 carbon atoms such as methanol, ethanol,isopropanol, tertiary butanol, etc., or from polyhydric alcohols such asethylene glycol, diethylene glycol, 2-methoxy ethanol,tri(1,2-propylene) glycol and the like.

Preferably R³ is hydrogen or methyl group, while R² is a lower alkene oraryl group (e.g., phenyl, tolyl, etc). Most preferably, R² in the aboveformula, is a lower alkylene group of up to 10 carbon atoms, such asethylene, propylene, methyl propylene, etc. When R² is such a loweralkylene group, it can be represented as --(R³)₂ CCH₂ - wherein each R³is independently as hereinbefore defined and the sulfo group is attacheddirectly to the unsubstituted methylene carbon atoms.

Specific non-limiting examples of the sulfo-nitrogen-containing olefiniccompounds useful in preparing the additives of the present invention areillustrated by the following (for convenience only the acid form isshown, since derivation of the corresponding esters, salts, etc., iswell within the skill of those of skill in the art): ##STR17## Specificexamples of related olefinic sulfonyl- and nitrogen-containingsubstrates wherein R² is a trivalent group, are the following (again,only the acid form is shown for convenience): ##STR18## Related olefinicsulfonyl- and nitrogen-containing compounds wherein R⁴ is a trivalentgroup, are the following: ##STR19##

The sulfo- and nitrogen-containing compounds used in the preparation ofthe additives of this invention are available from a number of sourcesknown to those of skill in the art. For example, a particularlypreferred substrate wherein R² is an alkylene group is available fromthe reaction of acryl chloride with an appropriate amino sulfonic acid.Alternatively, similar compounds can be produced by the reaction of analiphatic nitrile with a 1-olefin in the presence of a sulfating agentcomprised of a mixture of sulfuric acid and acid anhydride (e.g., SO₃)containing at least two moles of acidic anhydride per mole of sulfuricacid. One such reaction is represented by the general equation:

Ch₂ =cr₃ cn + ch₂ =cr₂ ³ + so₃.h₂ so₄ ch₂ =cr₃ c(o)nh -- ch₂ cr₂ so₃ h

further details about such reactions can be found in Canadian patent704,778 and U.S. Pat. Nos. 3,506,707 and 3,544,597, which are herebyincorporated by reference for their relevant disclosures.

Another class of preferred sulfonyl- and nitrogen-containing substrateshas two acryl olefinic bonds and a trivalent R⁴ group is convenientlyprepared by the reaction of an aldehyde having at least onealpha-hydrogen substituent (i.e., a hydrogen substituent on the carbonatom adjacent to the carbonyl bonded carbon atom), a nitrile and asulfonating agent. Preferably, the sulfonating agent is sulfur-trioxide,fuming sulfuric acid or sulfuric acid such as 98%, 96%, or 90% aqueoussulfuric acid. Chlorosulfonic acid or other well-known sulfonatingagents can also be used. Further details of this type of preparation areto be found in U.S. Pat. No. 3,531,442 which is hereby incorporated byreference for its relevant disclosures.

Generally, formation of the novel additives of this invention isachieved by contacting about 0.1 to about 1.0 moles of at least one ofthe afore-described phosphorus acid compounds with about 1 to about 0.1equivalent of at least one of the aforedescribed sulfo-,nitrogen-containing compounds (1 equivalent of the latter is themolecular weight of the sulfo compound divided by the number of terminalolefinic linkages present). The reaction normally is carried out for aperiod of 0.1 to 24, generally, 0.1 to 12 hours, at a temperature ofabout 15° C. up to the decomposition point of any component of thereaction mixture, preferably from 50° C. to 200° C.

Suitable substantially inert organic liquid solvents or diluents may beused in the reaction and include such relatively low boiling liquids ashexane, heptane, benzene, toluene, xylene, methanol, isopropanol, etc.,as well as high boiling materials such as solvent neutral oils, brightstocks and various types of synthetic and natural lubricating oil basestocks. Factors governing the choice and use of such materials are wellknown to those of skill in the art. Normally such a diluent will be usedto facilitate heat control, handling, filtration, etc. It is oftendesirable to select a diluent which will be compatible with the othermaterials, which are to be present in the environment where the productis intended to be used.

The inventive additives can be recovered from such solvent/diluents bysuch standard procedures as distillation, evaporation, precipitation,crystallization, dialysis, etc., when desired. Alternatively, if thesolvent/diluent is, for example, a base oil suitable for use in thefunctional fluid compositions of this invention, the product can be leftin the solvent/diluent and used to form the lubricating or functionalfluid composition as described below.

While it is possible to contact the phosphorus acid compounds andolefinic sulfo-, nitrogen-containing compounds in any order, it ispreferable to add the acid compound to the sulfo-, nitrogen-containingcompound in an appropriate solvent/diluent. It is also preferable, butnot essential, to use an alkali or alkaline earth metal salt of thephosphorus acid as the phosphorus acid compound.

The sulfo-, nitrogen-containing reaction products corresponding to theadditives of this invention can be represented by the following formulaewherein the --X-- atom is attached to either the carbon alpha or beta tothe amido group: ##STR20## wherein z is one or two, and R, R', R², R³,R⁴, X, Q, and y have the meanings ascribed to them in the abovedescription of the phosphorus acid and sulfo-nitrogen compounds of thisinvention. The additives of this invention include mixtures of two ormore different reaction products represented by the above formulae.

Naturally, the preferences set forth in the afore-going descriptions canbe incorporated into analogous formula. For example, a preferredcomposition of this invention can be represented by the formula:##STR21## wherein R and R' are C₁₋₁₀ alkyl groups and each R³ isindependently hydrogen or an aliphatic hydrocarbyl group, preferablyalkyl, of one to seven carbons.

EXAMPLES

The following non-limiting examples are specific preferred embodimentsof the present invention. All references to percentages, parts, etc., inthe present specification and appended claims refer to percentages,parts, etc., by weight unless expressly stated otherwise.

EXAMPLE 1

A mixture of 414 parts of 2-acrylamido-2-methylpropane-1 sulfonic acidand 600 parts of isopropanol at reflux temperature (85° C.) is slowlyadded over a five hour period to 1,648 parts of a fifty percent toluenesolution of sodium diisooctyl phosphorodithioate. Heating is continuedforan additional hour and the mixture stirred at room temperature foreighteenhours. Then 1,238 parts of diluent oil is added and the mixturestripped to110° C./3 mm. Filtration with the aid of 40 grams of filteraid provides an oil solution of the desired product which ischaracterized by a sulfur content of 6.56%, a phosphorus content of2.58% and a sodium content of 1.85%.

EXAMPLE 2

To a mixture of 704 parts of di(4-methyl secondary amyl)phosphorodithioic acid in 200 parts of methyl amyl alcohol is slowlyadded over seven hours at 80°-85° C., 414 parts of2-acrylamido-2-methylpropanesulfonic acid. After heating for a period often hours at 80°-90° C., the mixture is filtered through cloth andneutralized with 25% caustic liquid soda to a pH of 7. Strippingto 90°C./19 mm provides the desired product which is characterized by a sulfurcontent of 16.88%, a phosphorus content of 5.06%, a nitrogen content of2.56% and a sodium content of 5.70%.

EXAMPLE 3

A phosphorodithioic dialkyl acid is prepared by reacting P₂ S₅ (1mole)with 4 moles of a commercial mixture of synthetic mixture of cocoalcohols having a carbon chain length ranging between 14 and 18 carbons.The resulting acid is characterized by a phosphorus content of 0.93% andasulfur content of 10.01%. This acid is converted into a calcium salt bytreatment of 2150 parts of acid with 353 parts of calcium hydroxide. Thecalcium salt is characterized by a phosphorus content of 3.34% and asulfur content of 6.58%.

To 158 parts of the afore-described calcium salt at 80° C. isslowlyadded 68 parts of 2-acrylamido-1-octadecane sulfonic acid over 0.5hour. The mixture is held at 85°-90° C. for five hours and blown withnitrogen at a rate of 0.25 scfh (standard cubic feet per hour). Thefinal product is obtained as a filtrate by filtration with the aid of 7parts of filter aid at a temperature of below 90° C. and ischaracterized by a sulfur content of 6.57%, a nitrogen content of 0.96%and a phosphorus content of 2.29%.

EXAMPLE 4

To 151 parts of di(isooctyl)phosphorodithioic acid under a nitrogenatmosphere is added over 0.5 hour at 80° C., 72 parts of2-acrylamido-2-methylpropanesulfonic acid. To this mixture is added 150parts of isopropyl alcohol. The mixture is held at reflux for five hourswhile being sparged with nitrogen at 0.25 scfh. The reaction mixture isstored for eighteen hours at room temperature and is stripped to 70°C./30 mm over a period of 1.5 hours. Filtration with the aid offilteraid at a temperature under 90° C. provides the desired product as awhite, waxy solid being characterized by a sulfur content of 15.83%, anitrogen content of 2.10% and a phosphorus content of 5.45%.

EXAMPLE 5

To 1600 parts of a barium salt of the phosphorodithioic dialkyl esteracid described in Example 3 at 80° C. is added 300 parts of2-acrylamido-2-methylpropanesulfonic acid over a period of 0.25 hour.Reaction mixture is held at 80°-85° C. for eight hours whilebeing blownwith nitrogen at a rate of 1 to 2scfh. Stripping over a four hour periodto 90° C./30mm and filtration with the aid of 30 parts of filter aidprovides the desired product as a clear yellow liquid characterized by asulfur content of 6.85%, a nitrogen content of 1.06% and a phosphoruscontent of 2.43%.

EXAMPLE 6

A solution of 423 parts of O,O-di(2-ethylhexyl)-phosphoromonothioic acidin500cc parts by volume of petroleum naphtha is added to an oil solutionof 292 parts of the potassium salt of2-acrylamido-2-phenylethanesulfonic acid. The resulting mixture isstirred for two hours at 25°-50° C. and then stripped to 130° C./0.5mmto yield the desired product as a residue.

EXAMPLE 7

A mixture of 250 parts of diphenylphosphinic acid and an equal volume ofdiluent oil is added over a two hour period to a mixture of 278 parts of1,1-bis-(acrylamido)2-ethylpropyl-2-sulfonic acid and 500 parts ofdiluentoil. After stirring for two hours at 30° C., anhydrous ammonia isadded to the reaction mixture in an amount sufficient to neutralize allthe sulfonic acid groups. Cooling and the addition of pentane to themixture precipitates the ammonium salt of the desired product. Thisprecipitate is collected on a filter, washed with pentane and then driedat 45°-55° C. in vacuo to provide the final product.

EXAMPLE 8

One mole of the phosphorus acid compound described in Example 1 is addedtoa mixture of 0.5 mole of 1,2-bis(acrylamido)-4-phenylsulfonic acidcalcium salt and an equal volume of isopropanol. Reaction mixture isthen stirred for four hours and stripped to 120° C./5mm to provide thefinal product as a residue.

EXAMPLE 9

A mixture of 0.25 mole of the phosphorus acid compound described inExample3 and three volumes of isopropanol is added to 0.25 mole of1-acrylamido-4,5-naphthalene disulfonic acid zinc salt suspended in500ml of isopropanol over a period of two hours. The reaction mixture isthen stirred at 40°-60° C. and stripped to 100° C./10mm toprovide thefinal product as a residue.

EXAMPLE 10

The product of Example 3 was treated with a commercial mixture ofethylene polyamine corresponding in stoichiometry to tetraethylenepentamine to form the corresponding ammonium salt as the desiredproduct.

In one embodiment of this invention the products of the reaction of thephosphorus compound with the sulfo-, nitrogen-containing compounds arefurther reacted with a polyoxyalkylene glycol or epoxide to form anester of a glycol or polyoxyalkylene glycol. Suitable polyethers areethylene glycol, diethylene glycol, dipropylene glycol,tri(1,2-butylene)glycol, etc., including glycols containing up to thirtycarbon atoms. Suitable epoxides which yield similar products includethose having about two to about twenty carbon atoms and are exemplifiedby the following: ethylene oxide, propylene oxide, ethylenechlorohydrin, styrene oxide, butyl epoxy stearate, 1-tetradecene oxide,1-octadecene oxide, etc. Lower alkylene oxides (i.e., those containingless than eight carbon atoms) are preferred. Sulfur analogs of theabovedescribed epoxides (i.e., that is, thioepoxides or thiiranes) canalso be used alone or in admixture with theabove-described epoxides orglycols to form the corresponding thioanalogs of these esters.

Preferred glycols are those containing divalent ethylene or1,2-propylene group such as ethylene glycol, 1,2-propylene glycol, di-,tri-, tetra-, penta-, hexa-, etc.(oxyethylene)glycol, and the like.

Preferred epoxides are those which can be represented by the formula:##STR22##wherein each R³ is independently hydrogen or a C₁₋₇ lower alkylgroup. Typical of such epoxides are ethylene oxide, propylene oxide,1,2- and 2,3-butylene oxide and the like. Substituted epoxide such asepichlorohydrin can also be used.

Usually at least one mole of glycol or epoxide per equivalent ofsulfonic acid are used. Naturally, larger amounts of epoxide can be usedif it is desired to form poly(oxyalkylene)esters. Such reactions may becarried outat temperatures between about 0° C. up to the decompositiontemperature of the reaction mixture or one of its components, normallybetween about 15° C. and about 150° C. In epoxide reactions cooling maybe necessary to keep the reaction temperature within these ranges.

EXAMPLE 11

One mole of the product described in Example 1 in an oil diluent wasreacted with 5 moles of ethylene oxide to produce an ester ofpenta(oxyethylene)glycol.

EXAMPLES 12 and 13

In the same manner as described in Example 11, propylene oxide andbutylenethioepoxide were reacted with the products of Examples 2 and 3,respectively, to form the desired products.

As is noted above, the additive compositions of this invention areparticularly useful in water-oil emulsions which are to be used asfire-resistant hydraulic fluids. Generally, these emulsions are of theoil-in-water type where water is the continuous phase and oil thedispersed phase. However, the additives may also be employedadvantageously in water-in-oil emulsions. The oils in these emulsionscan be a hydrocarbon oil having a viscosity from about 40 SUS (SayboltUniversal Seconds) at 100° F. to 500 SUS at 210° F. Mineral oils havinglubricating viscosities (e.g., SAE 10 to 90, preferably SAE 50to 90,grade oils according to the standards set forth by the Society ofAutomotive Engineers) are especially advantageous for use in suchemulsions. Mixtures of oils from different sources are similarly useful.Such mixtures are available from mineral oils, vegetable oils, animaloils, synthetic oils of the silicone type, synthetic oils of thepolyolefin type, synthetic oils of the polyester type, and so forth.

The oil-water emulsion compositions of this invention comprise from 1 to80parts water, from about 20 to about 99 parts of oil and from about 0.1to about 20, preferably about 0.5 to about 15 parts of at least oneadditive composition according to this invention. Preferred emulsionshaving extremely desirable properties are composed of from 30 to 50parts water and from 50 to 70 parts oil, and the above-noted amount ofinventive additive. Emulsions intended specifically for use asfire-resistant hydraulic fluids should contain at least 30% water.

These emulsions can be prepared by simply mixing water, oil, anemulsifier (such as those described below), and the additives of thisinvention (and any other ingredients which are known in the art to bedesirable) in an homogenizer or any other efficient blending device.Heating the emulsion during or after its preparation is not necessary,though it may be preferred. The order of mixing the above-describedingredients is not critical although it is often convenient to firstprepare a concentrate comprising about 40 to about 95 parts of thevarious additives (such as the inventive additives) and from about 60 toabout 5 parts of a substantially inert liquid diluent or solvent andthen emulsifying the concentrate with water in the appropriateproportions. Usually the diluentor solvent will be oil which iscompatible with the oil to be used in the final emulsion but otherdiluents and solvents can be used.

Although the oil-water hydraulic fluid compositions of this inventiondescribed above are in themselves useful in many instances, they arenevertheless susceptible to improvement by the incorporation of variousother types of chemical additives, which impart the properties desiredforspecific applications. Emulsifiers such as the succinic acid estersdescribed in U.S. Pat. No. 3,281,356 are often helpful in forming theemulsions (the '356 patent is hereby incorporated by reference for itsrelevant disclosures in this regard). Emulsion stabilizers whichfunction to improve the stability of the emulsion against thedeterioration due to temperature, pressure, oxidation of the oil, andother harmful environments, are another type of useful additives. Amongsuch stabilizersare the phosphatides which are also described in detailin the aforementioned U.S. Pat. No. 3,281,356 at column 11. Thisdisclosure is hereby incorporated by reference for its relevant details.A particularly useful phosphatide is soybean lecithin which is describedin detail in "Encyclopedia of Chemical Technology", Kirk Othmer, Vol. 8,pages 309-326 (1952).

Other types of emulsion stabilizers have also been used, such asaliphatic glycols, monoethers, and fatty acid esters of such glycols,alkali and ammonium salts of sulfonic acids, neutral alkali metal saltsof fatty acids and other materials known to those of the art. A detaileddescription of such materials is given in the aforementioned U.S. Pat.No.3,281,356, which is hereby incorporated by reference in its entiretyfor its relevant disclosures.

When a stabilizer is used in the oil-water compositions of thisinvention, only a small amount is needed. It can be as little as about0.01 part and seldom exceeds about two parts per hundred parts of thetotal emulsion. Inmany instances, it is within the range of about 0.1 toabout 1 part per hundred parts of emulsion.

While the additives of the present invention are incorporated in thelubricating and hydraulic compositions of the invention as extremepressure, anti-wear and load-carrying agents, it may sometimes bedesirable to incorporate one or more additional agents to supplementtheiraction. Such supplemental agents may be illustrated by the lead,nickel or Group IIA and IIB metal phosphorodithioiate salts in which themetal may be magnesium, calcium, barium, strontium, zinc, cadmium, leador nickel. Zinc phosphorodithioates are particularly preferred. Othertypes of extreme pressure agents which can find use in the lubricatingoil compositions of this invention include chlorinated waxes, sulfurizedor phosphosulfurized fatty acid esters, di- or trihydrocarbyl phosphitesand phosphates, dihydrocarbon polysulfides and metal dithiocarbamates.These and other useful extreme pressure agents are described in moredetail in the books both entitled "Lubricant additives" by Smith andSmalheer (Published by the Lezius-Hiles Co., of Cleveland, Ohio) and byM. W. Raney(Published by the Noyes Data Corporation of Park Ridge, NewJersey) pages 146-212, both of which are incorporated herein byreference for their disclosure of additional extreme pressure agentswhich can be used in conjunction with the additives of the presentinvention.

Still another type of additive which can be useful in the lubricatingoil compositions of the present invention is rust-inhibiting agents. Oneor more rust-inhibiting agents can be used. The most effectiverust-inhibiting agents in the water-oil emulsions of this invention arealiphatic amines, especially aliphatic primary amines having at leasteight carbon atoms in the molecule. Preferably, such amines are tertiaryalkyl primary amines and have at the most thirty carbon atoms in themolecules. Other conventional rust-inhibiting agents can also be used,either alone or in combination with the amines discussed above.

Other conventional types of rust-inhibiting agents are salts of aromaticacids, such as benzoic acid, etc., with the afore-described amines.Hydroxy alkyl amines, particularly those with long chains, (i.e., C₈-C₃₀ aliphatic amines) containing one or two hydroxy alkyl substituentson the nitrogen atom are also useful as rust-inhibiting agents in thelubricating oil compositions of this invention. Nitric acid salts oflong-chained aliphatic amines such as those disclosed above aresimilarly useful.

The concentration of rust-inhibiting agent in the lubricating oilcompositions and particularly the oil-water emulsions of this inventiondepend to some extent upon the relative concentration of water in theemulsion. Ordinarily from about 0.1 part to 2 parts of rust-inhibitingagent per hundred parts of emulsion is sufficient.

The oil-water emulsions of this invention may also contain aconventional foam inhibitor such as a commercial dialkyl siloxanepolymer or polymer ofa methacrylate. Freezing point depressants (i.e.,water-soluble polyhydric alcohols such as glycerol or other polarsubstances such as the methyl ether of diethylene glycol) are alsouseful. The concentration of these additives is usually less than fiveparts per hundred parts of the oil-water emulsion.

Bacteriocides can also be included in the emulsions of this invention.These are illustrated by the nitro-bromo alkenes such as3-nitro-1-propylbromide, nitro-hydroxyalkanes, such astri(hydroxymethyl)nitromethane, 2-nitro-2-ethyl-1,3-propanediol and2-nitro-1-butanol and boric acid esters such as glycerol borate. Theconcentration of such bacteriocides usually range between about 0.001 toabout 1 part per hundred parts of the oil-in-water emulsion.

Oxidation inhibitors can also be included in the lubricating oilcompositions of this invention. Hindered phenols such as2,4-di-t-butyl-6-methyl phenol, 4,4'-methylene(2,6-di-t-pentyl phenol),and 2,6-di-t-octyl-4-secondary butyl phenol, are representative ofuseful oxidation inhibitors. The concentration of such oxidationinhibitors in the lubricating oil compositions of this invention isusually between about 0.01 to about 2 parts per hundred parts ofemulsion.

The following examples are illustrative of concentrates and oil-in-wateremulsion compositions of the present invention.

EXAMPLE 14 (emulsion)

    ______________________________________                                                                  Parts                                               Component                 by Weight                                           ______________________________________                                        Emulsifier*               9.0                                                 Soybean Lecithin          1.8                                                 Tertiary alkyl primary amine having a mol wt                                  of 191 in which the tertiary alkyl                                            radical is a mixture of radicals                                              having 11 to 14 carbon atoms.                                                                           0.6                                                 Product of Example 1      5.0                                                 SAE 40 mineral lubricating oil                                                                          284.0                                               Silicone anti-foam agent  0.0075                                              Water                                                                         ______________________________________                                        *Emulsifier made by reacting a polyisobutenyl succinic anhydride with          (isobutenyl group = M.sub.n 1000) with polyoxyethylene sorbitan               monooleate.                                                              

EXAMPLE 15 (concentrate)

    ______________________________________                                                                  Parts                                               Component                 by Weight                                           ______________________________________                                        Emulsifier of Example 14  9.0                                                 Soybean lecithin          1.8                                                 Tertiary alkyl primary amine having a mole-                                   cular weight of 330 in which the                                              tertiary alkyl radical is a mixture                                           of radicals having 18 to 24 carbon                                            atoms.                    0.6                                                 Lead diamyl dithiocarbamate                                                                             3.0                                                 Product of Example 3      3.0                                                 SAE 20 mineral lubricating oil                                                                          282.0                                               Silicone anti-foam agent  0.0045                                              ______________________________________                                    

EXAMPLE 16

    ______________________________________                                                                  Parts                                               Component                 by Weight                                           ______________________________________                                        Emulsifier of Example 14  18.0                                                Soybean lecithin          3.6                                                 Nitric acid salt of the tertiary alkyl                                        primary amine of Example 14                                                                             1.2                                                 Product of Example 2      18.0                                                4-methyl-2,6-di-t-butyl phenol                                                                          3.0                                                 SAE 5 mineral lubricating oil                                                                           534.0                                               Silicone anti-foam agents 0.015                                               Water                     400.0                                               ______________________________________                                    

EXAMPLE 17

    ______________________________________                                                                  Parts                                               Component                 by Weight                                           ______________________________________                                        The emulsifier of Example 14                                                                            45.0                                                The product of Example 8  18.7                                                Soybean lecithin          9.0                                                 Tertiary alkyl primary amine of Example 14                                                              3.0                                                 SAE 40 mineral lubricating oil                                                                          24.3                                                Silicone anti-foam agent  0.022                                               ______________________________________                                    

EXAMPLE 18

    ______________________________________                                                                  Parts                                               Component                 by Weight                                           ______________________________________                                        The product of Example 17 6.0                                                 SAE 40 mineral lubricating oil                                                                          94.0                                                ______________________________________                                    

As noted above, the lubricant compositions of this invention can also bebased on water-glycol mixtures. Such compositions usually comprise wateras a solvent and flame retarder, a water-soluble organic polymerthickenersuch as a polyoxyethylene polymer or an acrylated methacrylateester polymer, a water-miscible freezing point depressant, and smallamounts of such additives as the afore-described anti-rust agents,oxidation inhibitors, and so on, as well as the additive compositions ofthis invention. The water-miscible freezing point depressant is usuallya common glycol or glycol ether having from about 2 to 14 carbon atomssuch as ethylene glycol, diethylene glycol, triethylene glycol, ethyleneglycolethers, such as ethyl, methyl, propyl and butyl ethers thereof andsimilar ethers of diethylene glycol and triethylene glycol. In general,it is preferred to use simpler compounds such as represented by ethyleneglycol,propylene glycol, butylene glycol, and diethylene glycol for theyare cheap, easily obtainable and blend readily with water to give verylow freezing point mixtures which form the good basis for hydraulicfluid compositions.

Usually, the water content of such water-glycol mixtures is limited to amaximum of about 45 percent to be free from freezing problems. Theminimumamount of water is usually 10 percent also to avoid excessivelyhigh freezing points of the composition.

The preferred thickeners for use in these compositions are solubleorganic polymeric compounds usually copolymers of ethylene oxide and1,2-propyleneor 1,3-propylene oxide. A preferred one is one containingabout 75 mole percent ethylene oxide and about 25 mole percent ofpropylene oxide, copolymerized to a thick fluid polymer having a numberaverage molecular weight of about and not in excess of 15,000 to 20,000.Such polymers have viscosities of about 50,000 to about 100,000 SUS at100° F. Blends of such polymers may be used to achieve specificpurposes. All of the fore-described additives which are used in thewater-oil based hydraulic fluids can be used in appropriatecircumstances in the water-glycol fluids. Usually solubility andcompatibility dictate the choice of such additives which is within theskill of those skilled in the art.

The water-glycol based compositions of this invention contain 0.5 to 20parts of the additives of the invention per hundred parts of the totalmixture in addition to the glycol-water thickener and other notedadditives.

Exemplary of the water-glycol based compositions of this invention arethe following:

EXAMPLE 19

A mixture of equal weights of water and ethylene glycol is preparedcontaining as a thickener a copolymer of ethylene oxide and1,2-propylene oxide of number average molecular weight 15,000 having aviscosity of 50,000 SUS at 100° F., and 3 parts per hundred parts ofwater-glycol base of the product of Example 1.

EXAMPLE 20

A mixture of 33 parts by weight water and 67 parts by weight ethyleneglycol is prepared and treated with one part by weight per hundred partsof the copolymer of Example 19 and five parts by weight of the productof Example 3.

While the additives of this invention find particular use in theafore-described water-oil and water-glycol hydraulic fluids, they mayalsobe used in lubricating compositions containing only natural orsynthetic oils. Such usage is particularly favored when the additivecomposition is relatively non-polar, that is, it is an ester rather thana salt of free acid.

The additives of this invention can be effectively employed in a varietyoflubricating compositions based on diverse oils of lubricatingviscosity such as a natural or synthetic lubricating oil, or suitablemixtures thereof. The lubricating compositions contemplated includeprincipally crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines including automobile andtruck engines, two-cycle engine lubricants, aviation piston engines,marine and railroad diesel engines, and the like. However, automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulicfluids, and other lubricating oil andgrease compositions can benefit from the incorporation of the presentadditives.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lardoil) as well as solvent-refined or acid-refined mineral lubricatingoils ofthe paraffinic, naphthenic or mixed paraffinic-naphthenic types.Oils of lubricating viscosity derived from coal or shale are also usefulbase oils. Synthetic lubricating oils include hydrocarbon oils andhalo-substituted hydrocarbon oils such as polymerized andinterpolymerizedolefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, etc); alkyl benzenes(e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, etc.); and the like. Alkylene oxide polymers andinterpolymersand derivatives thereof where the terminal hydroxyl groupshave been modified by esterification, etherification, etc., constituteanother classof known synthetic lubricating oils. These are exemplifiedby the oils prepared through polymerization of ethylene oxide orpropylene oxide, the alkyl and aryl ethers of these polyoxyalkylenepolymers (e.g., methyl polyisopropyleneglycol ether having an averagemolecular weight of 1000, diphenyl ether of polyethylene glycol having amolecular weight of 500-1000, diethyl ether of polypropylene glycolhaving a molecular weight of 1000-1500, etc.) or mono- andpolycarboxylic esters thereof, for example, the acetic acid esters,mixed C₃ -C₈ fatty acid esters,or the C₁₃ Oxo acid diester oftetraethylene glycol. Another suitable class of synthetic lubricatingoils comprises the esters of dicarboxylic acids (e.g., phthalic acid,succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety ofalcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,2-ethylhexyl alcohol, pentaerythritol, etc.). Specific examples of theseesters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexylfumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the2-ethylhexyl diester of linoleic acid dimer, the complex ester formed byreacting one mole of sebacic acid with two moles of tetraethylene glycoland two moles of 2-ethyl-hexanoic acid, and the like. Silicon-based oilssuch as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxaneoils and silicate oils comprise another useful class of syntheticlubricants (e.g., tetraethyl silicate, tetraisopropyl silicate,tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-tetraethyl)silicate,tetra-(p-tert-butylphenyl)silicate,hexyl-(4-methyl-2-pentoxy)disiloxane,poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.). Othersynthetic lubricating oils include liquid esters ofphosphorus-containing acids (e.g., tricresyl phosphate, trioctylphosphate, diethyl ester of decane phosphonic acid, etc.), polymerictetrahydrofurans, and the like.

The lubricating oil compositions of this invention comprise a majoramount of oil and a minor, load-carrying improving amount of at leastone additive composition of the invention. Generally, this amount willbe about 0.5 to about 20 parts additive per hundred parts oil.

Exemplary of these lubricating oil compositions are the following:

EXAMPLE 21

A mixture of 95 parts of SAE 40 oil and 5 parts of the additivecompositionof Example 10.

EXAMPLE 22

A mixture of 90 parts of SAE lOW/30 oil, 7 parts of the additivecomposition of Example 3 and 3 parts of 2,4-di-t-butyl-6-methyl phenolin an antioxidant.

As indicated above during the description of the oil-water emulsions ofthis invention, it is often convenient to form concentrates of theadditives of this invention prior to incorporation of the additives inan emulsion composition. Such concentrates comprise about 40 to about 95parts additive and about 60 to about 5 parts of substantially inertorganic liquid diluents or solvents and are equally useful in preparingthe lubricating oil composition of this invention. Analogousglycol-based concentrates comprising about 50 to about 95 parts additivecomposition and about 50 to about 5 parts of at least one glycol orglycol-ether are equally useful. Remarks made hereinbefore in regard toconcentrates are applicable here.

What is claimed is:
 1. A hydraulic fluid comprising an oil-in-wateremulsion of 1 to 80 parts water, about 20 to about 99 parts oil andabout 0.1 to about 20 parts of at least one sulfur-, nitrogen- andphosphorus-containing additive made by reacting one or more phosphorusacid compounds of the formula ##STR23## wherein each X is independentlyoxygen or divalent sulfur, M is a hydrogen, an equivalent of a metal orammonium cation, R is hydrogen or a hydrocarbyl, hydrocarbyloxy, orhydrocarbyl mercapto group of about one to about thirty carbon atoms,and R' is XM or R, with the proviso that the total number of carbonatoms in both R and R' is at least two, with(B) one or more sulfo- andnitrogen-containing compounds of the general formulae ##STR24## whereiny is one or two, each R³ is independently hydrogen or lower alkyl groupof one to seven carbon atoms, R² is di- or trivalent hydrocarbyl grouphaving one to eighteen carbon atoms, R⁴ is a trivalent hydrocarbyl grouphaving one to eighteen carbon atoms, and Q is selected from the groupconsisting of --OH, --OR³, --OM, ----O(Alkylene-O)_(n) --R³, --N(R³)₂,--NR³ (Alkylene-NR³)_(n) R³, --OH(R³)₄, and --O⁻ N⁺ R₃ ³--(Alkylene-NR³)_(n) R³, wherein n has an average value of about one toabout ten, M is as defined in (A) and the alkylene group has from one toten carbon atoms.
 2. A hydraulic fluid comprising an oil-in-wateremulsion of 1 to 80 parts water, about 20 to about 99 parts oil andabout 0.1 to about 20 parts of at least one sulfo-, nitrogen- andphosphorus-containing additive selected from those corresponding to theformulae: ##STR25## and mixtures of two or more such additives wherein zis one or two, R, R', R², R³, R⁴, X, Q and y are as set forth inclaim
 1. 3. The fluid of claim 1 wherein R' is the same as R and R is ahydrocarbyloxy group containing one to about eighteen carbon atoms andeach X is oxygen.
 4. The fluid of claim 2 wherein R' is the same as Rand R is a hydrocarbyloxy group containing one to about eighteen carbonatoms and each X is oxygen.
 5. The fluid of claim 1 wherein each X is adivalent sulfur atom and R and R' are independently C₁ -C₁₈ alkoxygroups.
 6. The fluid of claim 1 wherein (B) is of the general formula##STR26##
 7. The fluid of claim 1 wherein M is a Group I, II(A) or II(B)metal cation.
 8. The fluid of claim 1 wherein Q is selected from thegroup consisting of --NR³ (Alkylene-NR³)_(n) R³ and --O^(-N) ^(+R) ₃ ³-(Alkylene-NR³)_(n) R³ and mixtures thereof.
 9. The fluid of claim 2wherein Q is selected from the group consisting of --NR³(Alkylene-NR³)_(n) R³ and --O^(-N) ^(+R) ₃ ³ -(Alkylene-NR³)_(n) R³ andmixtures thereof.
 10. The fluid of claim 1 wherein Q is--O(Alkylene-O)_(n) R³.
 11. The fluid of claim 2 wherein Q is--O(Alkylene-O)_(n) R³.
 12. A hydraulic fluid comprising a glycol-watermixture of about 10 to 45 percent water and 0.5 to 20 parts per hundredparts of the total mixture of at least one sulfur-, nitrogen- andphosphorus-containing additive made by reacting one or more phosphorusacid compounds of the formula ##STR27## wherein each X is independentlyoxygen or divalent sulfur, M is a hydrogen, an equivalent of a metal orammonium cation, R is hydrogen or a hydrocarbyl, hydrocarbyloxy, orhydrocarbyl mercapto group of about one to about thirty carbon atoms,and R' is XM or R, with the proviso that the total number of carbonatoms in both R and R' is at least two, with(B) one or more sulfo- andnitrogen-containing compounds of the general formulae ##STR28## whereiny is one or two, each R³ is independently hydrogen or lower alkyl groupof one to seven carbon atoms, R² is di- or trivalent hydrocarbyl grouphaving one to eighteen carbon atoms, R⁴ is a trivalent hydrocarbyl grouphaving one to eighteen carbon atoms, and Q is selected from the groupconsisting of --OH, --OR³, --OM, --O(Alkylene-O)_(n) -R³, --N(R³)₂,--NR³ (Alkylene-NR³)_(n) R³, --OH(R³)₄, and --O^(-N) ^(+R) ₃ ³-(Alkylene-NR³)_(n) R³, wherein n has an average value of about one toabout ten, M is as defined in (A) and the alkylene group has from one toten carbon atoms.
 13. A hydraulic fluid comprising a glycol-watermixture of about 10 to 45 percent water and 0.5 to 20 parts per hundredparts of the total mixture of at least one sulfo-, nitrogen- andphosphorus-containing additive selected from those corresponding to theformulae: ##STR29## and mixtures of two or more such additives wherein zis one or two, R, R', R², R³, R⁴, X, Q and y are set forth in claim 12.14. The fluid of claim 12 wherein R' is the same as R and R is ahydrocarbyloxy group containing one to about eighteen carbon atoms andeach X is oxygen.
 15. The fluid of claim 13 wherein R' is the same as Rand R is a hydrocarbyloxy group containing one to about eighteen carbonatoms and each X is oxygen.
 16. The fluid of claim 12 wherein each X isa divalent sulfur atom and R and R' are independently C₁ -C₁₈ alkoxygroups.
 17. The fluid of claim 12 wherein (B) is of the general formula##STR30##
 18. The fluid of claim 12 wherein M is a Group I, II(A) orII(B) metal cation.
 19. The fluid of claim 12 wherein Q is selected fromthe group consisting of -NR³ (Alkylene-NR³)_(n) R³ and --O^(-N) ^(+R) ₃³ -(Alkylene-NR³)_(n) R³ and mixtures thereof.
 20. The fluid of claim 13wherein Q is selected from the group consisting of -NR³(Alkylene-NR³)_(n) R³ and --O^(-N) ^(+R) ₃ ³ -(Alkylene-NR³)_(n) R³ andmixtures thereof.
 21. The fluid of claim 13 wherein Q is-O(Alkylene-O)_(n) R³.
 22. The fluid of claim 12 wherein Q is-O(Alkylene-O)_(n) R³.
 23. The fluid of claim 1 wherein R' is the sameas R and R is a hydrocarbyloxy group of one to about 18 carbon atoms andeach X is sulfur.
 24. The fluid of claim 2 wherein R' is the same as Rand R is a hydrocarbyloxy group of one to about 18 carbon atoms and eachX is sulfur.
 25. The fluid of claim 12 wherein R' is the same as R and Ris a hydrocarbyloxy group of one to about 18 carbon atoms and each X issulfur.
 26. The fluid of claim 13 wherein R' is the same as R and R is ahydrocarbyloxy group of one to about 18 carbon atoms and each X issulfur.